CN105098121B - Diaphragm, preparation method thereof and lithium ion battery using diaphragm - Google Patents
Diaphragm, preparation method thereof and lithium ion battery using diaphragm Download PDFInfo
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- CN105098121B CN105098121B CN201410153381.7A CN201410153381A CN105098121B CN 105098121 B CN105098121 B CN 105098121B CN 201410153381 A CN201410153381 A CN 201410153381A CN 105098121 B CN105098121 B CN 105098121B
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Abstract
The invention discloses a diaphragm, a preparation method thereof and a lithium ion battery using the diaphragm, wherein the diaphragm comprises a porous diaphragm substrate and a composite coating coated on at least one surface of the diaphragm substrate, the composite coating comprises a polymer wax-coated modified hydroxyl-containing superfine glass fiber and water-based latex, and the melting point of the polymer wax used for coating the hydroxyl-containing superfine glass fiber is 80-160 ℃; the preparation method is used for preparing the diaphragm. Compared with the prior art, the diaphragm has the advantages of high thermal stability, strong mechanical property, strong liquid absorption capability, good safety performance and the like, so that the cycle performance and the safety performance of the lithium ion battery can be effectively improved.
Description
Technical field
The invention belongs to technical field of lithium ion, it is more particularly related to it is a kind of have good circulation and
Membrane of security performance and preparation method thereof.
Background technology
There is high energy density, operating voltage height, memory-less effect and the chemistry having extended cycle life as one kind
Battery, the lithium ion battery battery as used in mobile phone, laptop, digital camera and portable small-sized electric appliance, is progressively moved towards
The energy field of traffic battery such as electric vehicle, energy-accumulating power station.With widening for lithium ion battery applications field, price into
Originally, security performance and cycle life etc. also increasingly attract attention.
Lithium ion battery separator (LIBS) is the important set in battery in addition to positive electrode, negative material and electrolyte
Into part, it plays the important function isolated positive and negative anodes and realize electronic isolation and ion conducting；Since membrane is a kind of high
Added value material, therefore how on the basis of its security is ensured, it is all important to reduce Costco Wholesale and improve cycle life
Research direction.
At present, commercialized lithium ion battery separator is mostly polyalkene diaphragm, but when battery temperature raises, it is this every
Film can occur thermal contraction and even melt and bring security risk.In view of the above-mentioned problems, the solution of this field is on membrane
One layer of ceramic layer material is coated with, to play the effect for reducing thermal contraction, preventing positive and negative anodes short circuit.It is it is to be noted that ceramic
Although coating membrane can improve the thermal stability and security performance of battery, but also affect the cycling of battery and forthright again
Energy；Further, since ceramic material has the characteristics that hardness is big, thus its coating process to the loss of carving knife and applicator roll very
Greatly, and be generally difficult to ensure long-time coating thickness homogeneity；Furthermore the price of ceramic slurry is comparatively higher, no
Beneficial to reducing cost.
The content of the invention
It is an object of the invention to：It provides a kind of with good circulation and the membrane of security performance and relative inexpensiveness
And preparation method thereof and using the membrane lithium ion battery, to overcome defect existing in the prior art.
In order to realize foregoing invention purpose, the present invention provides a kind of membrane, including porous diaphragm matrix and coating
Composite coating at least one surface of diaphragm matrix, the composite coating contain hydroxyl including polymer-wax coating modification
Ultra-fine fibre glass and water based emulsion, for coat the fusing point of the polymer-wax of the ultra-fine fibre glass containing hydroxyl for 80~
160℃。
Compared with existing ceramic coating technique, the composite coating that the present invention is coated on diaphragm matrix surface can not only carry
The thermal stability and mechanical performance of high diaphragm matrix reduce slurry and equipment cost, and it contains the superfine glass fibre of hydroxyl
It is the liquid-adsorption layer for having larger aperture to tie up the skeleton being woven into, it is thus possible to receive more electrolyte, be conducive to improve battery core
Multiplying power and cycle performance；Moreover, when battery because overcharging when abuses make its internal temperature reach the fusing point of polymer-wax, coat
Polymer-wax on the ultra-fine fibre glass surface containing hydroxyl can be melted, and be inhaled into due to capillarity containing hydroxyl
Ultra-fine fibre glass layer and diaphragm matrix micropore in play the function of closed pore open circuit, lead to so as to effectively cut off lithium ion
Road ensures the safety of battery.
As a kind of improvement of membrane of the present invention, the ultra-fine fibre glass containing hydroxyl of the polymer-wax coating modification
Content in composite coating is 60~95.5wt.%, and content of the water based emulsion in composite coating is 4~30wt.%.
As a kind of improvement of membrane of the present invention, the ultra-fine fibre glass containing hydroxyl is with certain hydroxyl
Commercially ultra-fine fibre glass, a diameter of 0.5~5 μm, length is 0.1~5mm.This is because commercially ultra-fine fibre glass is general
By coupling agent treatment with a certain amount of hydroxyl, therefore it is easy to and the functional groups phase interaction in polymer-wax lotion
With forming cladded type structure, while polymer-wax can also increase the compatible of the ultra-fine fibre glass containing hydroxyl and diaphragm matrix
Property, so as to more effectively combine the effect of the ultra-fine fibre glass containing hydroxyl and both polymer.
The bag formed as a kind of improvement of membrane of the present invention, polymer-wax on the ultra-fine fibre glass surface containing hydroxyl
Coating thickness is 1~5 μm.
As a kind of improvement of membrane of the present invention, the molecular weight of the polymer-wax is 5000~30000.
As a kind of improvement of membrane of the present invention, average grain diameter of the polymer-wax before cladding is 0.1~5 μm.This
It is in order to ensure that its particle is more than the aperture of diaphragm matrix, to avoid dropping that invention, which has the average grain diameter of polymer-wax required,
Polymer-wax particle the micropore of diaphragm matrix is blocked in normal use, cause lithium ion influences battery by obstructed
Normal use.Since the aperture of diaphragm matrix is generally between 10~100nm, the superfine glass containing hydroxyl of selection
The diameter of fiber and polymer-wax can be more than the aperture of membrane.
As a kind of improvement of membrane of the present invention, the polymer-wax is selected from polyethylene wax, polypropylene wax, polyethylene glycol oxide
At least one of wax, modified polyethylene wax, modified polypropylene waxes and ethylene-propylene copolymer wax.The modified polypropylene waxes
It can be polytetrafluoroethylmodified modified polypropylene wax and polytetrafluoroethylmodified modified polyethylene wax with modified polyethylene wax, but be not limited to
This.
As a kind of improvement of membrane of the present invention, the water based emulsion be selected from styrene-acrylic latex, pure third latex, butadiene-styrene latex,
At least one of polyvinylidene fluoride and ethylene-vinyl acetate copolymer.
As a kind of improvement of membrane of the present invention, the composite coating further includes the water soluble polymer of 0.5~10wt.%
Thickener.It is to enhance the stability of coating paste to add in thickener, and ensures the good dispersiveness of coating paste.
As a kind of improvement of membrane of the present invention, the water soluble polymer thickener is selected from sodium carboxymethylcellulose, carboxylic
At least one of ethyl cellulose, sodium alginate, polyacrylamide and polyvinyl alcohol.
As a kind of improvement of membrane of the present invention, the thickness of the composite coating is 2~5 μm.If because composite coating
Thickness it is too small, can not play the role of reducing diaphragm retracts and lithium ion tunnel is cut off during over-charging of battery；If apply thickness
Degree is too big, then can influence the migration of lithium ion during normal use to a certain extent, so influence battery cycle performance and times
Rate performance.
As a kind of improvement of membrane of the present invention, coating is one kind in single side coating or dual coating.In contrast, adopt
It can play the role of better safeguard protection with coated on both sides.
As a kind of improvement of membrane of the present invention, the diaphragm matrix is polyethylene film, polypropylene screen, polypropylene/poly- second
Alkene/polypropylene composite film, PVDF membrane, polyethylene/polyvinylidene fluoride composite membrane, polypropylene/polyvinylidene fluoride
One kind in composite membrane, aramid fiber film and polyimide film, thickness are 5-30 μm.
As a kind of improvement of membrane of the present invention, the fusing point of the polymer-wax is 100~150 DEG C.The present invention is to polymerization
The fusing point of object wax has the reason for required to be：The Self-closed hole temperature of general polyethylene (PE) film is about 130 DEG C, polypropylene (PP) film
Self-closed hole temperature be about 160 DEG C, PVDF membrane Self-closed hole temperature is at 170 DEG C or so, polyethylene/polyvinylidene fluoride
Between 130 DEG C~170 DEG C, the Self-closed hole temperature of polypropylene/polyvinylidene fluoride composite membrane exists the Self-closed hole temperature of composite membrane
Between 160 DEG C~170 DEG C, and aramid fiber film, polyimide film do not have Self-closed hole function then, and heat decomposition temperature is at 300 DEG C or more；
When internal temperature of battery reaches 100 DEG C or so, PE, PP membrane just have certain contraction, so as to cause short-circuit risks；Polymerization
The fusing point selection of object wax needs to ensure that it can be melted simultaneously before Self-closed hole or thermal decomposition occur for the polyvinyls such as PE or PP base material
Be drawn by capillarity in the ultra-fine fibre glass containing hydroxyl and the micropore of diaphragm matrix, can just effectively cut off lithium from
Subchannel ensures the safety of battery.
In order to realize foregoing invention purpose, the present invention also provides a kind of sides for preparing membrane described in any of the above-described paragraph
Method comprises the following steps：
1) ultra-fine fibre glass containing hydroxyl is proportionally added into the polymer-wax lotion that solid content is 20~50%
In, after stirring and impregnating fully, filtration drying obtains the ultra-fine fibre glass containing hydroxyl of polymer-wax coating modification；
2) water and water soluble polymer thickener are proportionally added into mixer grinder, are completely dissolved thickener,
Obtain the aqueous solution of thickener；
3) ultra-fine fibre glass containing hydroxyl by polymer-wax coating modification made from step 1) is proportionally added into
In aqueous thickener solution made from step 2), primary slurry is obtained after stirring；
4) water based emulsion is added in into the primary slurry that step 3) obtains, filters, obtain through 150 mesh filter screens after stirring evenly
Coating paste；
5) coating paste that step 4) obtains is coated in diaphragm matrix by way of intaglio printing or extrusion coated
Surface obtains membrane after drying.
As a kind of improvement of membrane preparation method of the present invention, coating paste is coated in porous matrix in the step 5)
When contact angle be less than 90 °, obtain the membrane of uniform coating thickness.
In order to realize foregoing invention purpose, the present invention also provides a kind of lithium ion battery, including positive plate, negative plate
And the membrane between adjacent positive piece and negative plate is interval in, the membrane is the membrane described in any of the above-described paragraph.
Compared with the prior art, the present invention adds in the superfine glass containing hydroxyl of polymer-wax cladding in coating paste
Fiber and water based emulsion not only can preferably reduce the contraction of diaphragm matrix, ensure security of the battery under overcharge conditions
Can, and since fiber reinforcement has the liquid-adsorption layer of larger aperture, more electrolyte can be received；In addition, it is coated on
The polymer-wax organic matter of fiber surface with respect to inorganic oxide aluminium for, polymer-wax and electrolyte have better compatibility,
It can absorb and be swollen and retain more electrolyte, so advantage is had more on cycle performance, so as to be conducive to improve following for battery
Ring performance；Furthermore the superfine glass containing hydroxyl that coating paste of the invention is used water as solvent, coated with polymer-wax
Fiber is as solid filler, therefore not only safety and environmental protection, but also can reduce slurry and equipment cost, have it is simple and practicable,
The advantages of being easily industrialized production.
Description of the drawings
Below in conjunction with the drawings and specific embodiments to membrane of the present invention and preparation method thereof, the lithium ion using the membrane
Battery and its advantage are further elaborated.
Fig. 1 is the diaphragm closed pore temperature test monitoring graph of Examples 1 to 3 and comparative example 1 in the present invention.
Fig. 2 is the cycle performance of battery graph of Examples 1 to 3 and comparative example 1~3 in the present invention.
Fig. 3~6 are that number is that the 1C/6V of battery of D1, S1, S2, S3 overcharge monitoring curve in the present invention.
Specific embodiment
In order to which the goal of the invention, technical solution and the advantageous effects that make the present invention become apparent from, with reference to embodiments,
The present invention will be described in further detail.It should be appreciated that the embodiment described in this specification is merely to explain this
Invention, is not intended to limit the present invention, formula, ratio of embodiment etc. can adaptation to local conditions make a choice and essence had no to result
Property influence.
Embodiment 1
The preparation process of the present embodiment membrane is：
1) it is the ultra-fine fibre glass containing hydroxyl in mass ratio 1 of 1000nm by average diameter:10 ratio is added to
(average grain diameter of polyethylene wax is 0.5 μm to the polythene wax emulsion that solid content is 25%, and fusing point is 105 DEG C, and molecular weight is
5000, solvent is deionized water) in, after stirring and impregnating 60min, filtration drying obtains polyethylene wax coating thickness as 2 μm
The ultra-fine fibre glass containing hydroxyl；
2) by water and water-soluble sodium carboxymethylcellulose in mass ratio 98.5:1.5 are added in mixer grinder, make carboxylic
Sodium carboxymethylcellulose pyce is completely dissolved, and obtains the aqueous solution of sodium carboxymethylcellulose；
3) ultra-fine fibre glass containing hydroxyl that polyethylene wax coats is proportionally added into sodium carboxymethylcellulose water
In solution, primary slurry is obtained after stirring；
4) styrene-acrylic latex is added in into primary slurry, the strainer filtering through 150 mesh after stirring evenly obtains coating paste；
The quality of polyethylene wax coats in coating paste the ultra-fine fibre glass containing hydroxyl, pure third latex and sodium carboxymethylcellulose
Than for 85:10:5；
5) obtained coating paste is coated in the polyethylene table of 12 μ m-thicks using dual coating by intaglio printing mode
Face, single side coating thickness are 3 μm, and membrane is obtained after drying.
Membrane made from the present embodiment include the polyethylene film matrix that thickness is 12 μm and be coated on 3 μm of matrix two sides it is multiple
Close coating；Composite coating includes the ultra-fine fibre glass (bag of polyethylene wax containing hydroxyl that the polyethylene wax of 85wt.% coats
Coating thickness is 2 μm), the sodium carboxymethylcellulose of the styrene-acrylic latex of 10wt.% and 5wt.%；Wherein, containing the ultra-fine of hydroxyl
The average diameter of glass fibre is 1000nm, and the fusing point of polyethylene wax is 105 DEG C, and molecular weight 5000, average grain diameter is 0.5 μ
m。
Embodiment 2
The preparation process of the present embodiment membrane is：
1) it is the ultra-fine fibre glass containing hydroxyl in mass ratio 1 of 500nm by average diameter:20 ratio is added to solid
Polythene wax emulsion that content is 30% (average grain diameter of polyethylene wax is 0.5 μm, and fusing point is 110 DEG C, molecular weight 8000,
Solvent is deionized water) in, after stirring and impregnating 60min, filtration drying obtains polyethylene wax coating thickness and is 1 μm containing
The ultra-fine fibre glass of hydroxyl；
2) by water and water-soluble carboxyethyl cellulose in mass ratio 98.5:1.5 are added in mixer grinder, make carboxylic first
Base sodium cellulosate is completely dissolved, and obtains the aqueous solution of sodium carboxymethylcellulose；
3) ultra-fine fibre glass containing hydroxyl that polyethylene wax coats is proportionally added into sodium carboxymethylcellulose water
In solution, primary slurry is obtained after stirring；
4) styrene-acrylic latex is added in into primary slurry, the strainer filtering through 150 mesh after stirring evenly obtains coating paste；
The quality of polyethylene wax coats in coating paste the ultra-fine fibre glass containing hydroxyl, styrene-acrylic latex and sodium carboxymethylcellulose
Than for 85:10:5；
5) obtained coating paste is coated in the polyethylene film of 12 μ m-thicks using dual coating by extrusion coated mode
Matrix surface, single side coating thickness are 2 μm, and membrane is obtained after drying.
Membrane made from the present embodiment include the polyethylene film matrix that thickness is 12 μm and be coated on 2 μm of matrix two sides it is multiple
Close coating；Composite coating includes the ultra-fine fibre glass (bag of polyethylene wax containing hydroxyl that the polyethylene wax of 85wt.% coats
Coating thickness is 1 μm), the sodium carboxymethylcellulose of the styrene-acrylic latex of 10wt.% and 5wt.%；Wherein, ultra-fine fibre glass
Average diameter is 500nm, and the fusing point of polyethylene wax is 110 DEG C, and molecular weight 8000, average grain diameter is 0.5 μm.
Embodiment 3
The preparation process of the present embodiment membrane is：
1) it is the ultra-fine fibre glass containing hydroxyl in mass ratio 1 of 500nm by average diameter:20 ratio is added to solid
(average grain diameter of polypropylene wax is 1 μm to the polypropylene wax emulsion that content is 25%, and fusing point is 120 DEG C, and molecular weight 8000 is molten
Agent is deionized water) in, after stirring and impregnating 60min, filtration drying obtains polypropylene wax coating thickness and is 1 μm containing hydroxyl
The ultra-fine fibre glass of base；
2) by water and water-soluble sodium carboxymethylcellulose in mass ratio 98.5:1.5 are added in mixer grinder, make carboxylic
Sodium carboxymethylcellulose pyce is completely dissolved, and obtains the aqueous solution of sodium carboxymethylcellulose；
3) ultra-fine fibre glass containing hydroxyl that polypropylene wax coats is proportionally added into sodium carboxymethylcellulose water
In solution, primary slurry is obtained after stirring；
4) styrene-acrylic latex is added in into primary slurry, the strainer filtering through 150 mesh after stirring evenly obtains coating paste；
The quality of polypropylene wax coats in coating paste the ultra-fine fibre glass containing hydroxyl, styrene-acrylic latex and sodium carboxymethylcellulose
Than for 80:15:5；
5) obtained coating paste is coated in the polypropylene screen of 12 μ m-thicks using dual coating by intaglio printing mode
Matrix surface, single side coating thickness are 2 μm, and membrane is obtained after drying.
Membrane made from the present embodiment include the polypropylene screen matrix that thickness is 12 μm and be coated on 2 μm of matrix two sides it is multiple
Close coating；Composite coating includes the ultra-fine fibre glass (bag of polypropylene wax containing hydroxyl that the polypropylene wax of 80wt.% coats
Coating thickness is 1 μm), the sodium carboxymethylcellulose of the styrene-acrylic latex of 15wt.% and 5wt.%；Wherein, containing the ultra-fine of hydroxyl
The average diameter of glass fibre is 500nm, and the fusing point of polypropylene wax is 120 DEG C, and molecular weight 8000, average grain diameter is 1 μm.
Embodiment 4
The preparation process of the present embodiment membrane is：
1) it is the ultra-fine fibre glass containing hydroxyl in mass ratio 1 of 2500nm by average diameter:20 ratio is added to
(average grain diameter of polyethylene glycol oxide wax is 2 μm to the polyethylene glycol oxide wax emulsion that solid content is 40%, and fusing point is 80 DEG C, molecular weight
For 5000, solvent is deionized water) in, after stirring and impregnating 60min, filtration drying obtains polyethylene glycol oxide wax coating thickness
For 2 μm of the ultra-fine fibre glass containing hydroxyl；
2) by water and water-soluble carboxyethyl cellulose in mass ratio 98.5:1.5 are added in mixer grinder, make carboxylic second
Base cellulose is completely dissolved, and obtains the aqueous solution of carboxyethyl cellulose；
3) ultra-fine fibre glass containing hydroxyl for coating polyethylene glycol oxide wax is proportionally added into carboxyethyl cellulose
In aqueous solution, primary slurry is obtained after stirring；
4) pure third latex is added in into primary slurry, the strainer filtering through 150 mesh after stirring evenly obtains coating paste；
The matter of polyethylene glycol oxide wax coats in coating paste the ultra-fine fibre glass containing hydroxyl, pure third latex and carboxyethyl cellulose
Amount is than being 90:8:2；
5) obtained coating paste is coated in the aramid fiber membrane of 14 μ m-thicks using single side coating by intaglio printing mode
Surface, single side coating thickness are 4 μm, and membrane is obtained after drying.
Membrane made from the present embodiment includes the aramid fiber film matrix and be coated on the 4 of aramid fiber film matrix one side that thickness is 14 μm
μm composite coating；Composite coating includes the ultra-fine fibre glass (polyoxy containing hydroxyl that the polyethylene glycol oxide wax of 90wt.% coats
The coating thickness for changing ethylene waxes is 2 μm), pure third latex of 8wt.% and the carboxyethyl cellulose of 2wt.%；Wherein, containing hydroxyl
The average diameter of the ultra-fine fibre glass of base is 2500nm, and the fusing point of polyethylene glycol oxide wax is 80 DEG C, and molecular weight 5000 is average
Grain size is 2 μm.
Embodiment 5
The preparation process of the present embodiment membrane is：
1) it is the ultra-fine fibre glass containing hydroxyl in mass ratio 1 of 1000nm by average diameter:10 ratio is added to
(average grain diameter of polyethylene wax is 0.1 μm to the polythene wax emulsion that solid content is 40%, and fusing point is 120 DEG C, and molecular weight is
15000, solvent is deionized water) in, after stirring and impregnating 60min, filtration drying obtains polyethylene wax coating thickness as 0.5
μm the ultra-fine fibre glass containing hydroxyl；
2) by water and water-soluble sodium alginate in mass ratio 98.5:1.5 are added in mixer grinder, make sodium alginate
It is completely dissolved, obtains the aqueous solution of sodium alginate；
3) ultra-fine fibre glass containing hydroxyl that polyethylene wax coats is proportionally added into sodium alginate aqueous solution,
Primary slurry is obtained after stirring；
4) butadiene-styrene latex is added in into primary slurry, the strainer filtering through 150 mesh after stirring evenly obtains coating paste；
The mass ratio of the ultra-fine fibre glass containing hydroxyl of polyethylene wax cladding, butadiene-styrene latex and sodium alginate is in coating paste
77:15:8；
5) obtained coating paste is coated in the polyimides of 16 μ m-thicks using dual coating by intaglio printing mode
Matrix surface, single side coating thickness are 1 μm, and membrane is obtained after drying.
Membrane made from the present embodiment includes the polyimide film matrix and be coated on polyimide film base that thickness is 16 μm
1 μm of composite coating on body two sides；Composite coating includes the ultra-fine fibre glass containing hydroxyl that the polyethylene wax of 77wt.% coats
The sodium alginate of (coating thickness of polyethylene wax is 0.5 μm), the butadiene-styrene latex of 15wt.% and 8wt.%；Wherein, containing hydroxyl
The average diameter of the ultra-fine fibre glass of base is 1000nm, and the fusing point of polyethylene wax is 120 DEG C, molecular weight 15000, average grain
Footpath is 0.1 μm.
Embodiment 6
The preparation process of the present embodiment membrane is：
1) it is the ultra-fine fibre glass containing hydroxyl in mass ratio 1 of 500nm by average diameter:10 ratio is added to solid
(average grain diameter of polypropylene wax is 1 μm to the polypropylene wax emulsion that content is 30%, and fusing point is 130 DEG C, and molecular weight 10000 is molten
Agent is deionized water) in, after stirring and impregnating 60min, filtration drying obtains polypropylene wax coating thickness and is 2 μm containing hydroxyl
The ultra-fine fibre glass of base；
2) by water and water soluble polymer thickener (mixture of polyvinyl alcohol and sodium carboxymethylcellulose, the matter of the two
Amount is than being 1:1) in mass ratio 98.5:1.5 are added in mixer grinder, are completely dissolved it, obtain macromolecule thickener water
Solution；
3) to be proportionally added into macromolecule thickener water-soluble for the ultra-fine fibre glass containing hydroxyl for coating polypropylene wax
In liquid, primary slurry is obtained after stirring；
4) water based emulsion (mixture of polyvinylidene fluoride and pure third latex, the quality of the two are added in into primary slurry
Than for 1:1) strainer filtering through 150 mesh after, stirring evenly, obtains coating paste；What polypropylene wax coated in coating paste contains
The mass ratio for having the ultra-fine fibre glass of hydroxyl, water based emulsion and macromolecule thickener is 60:30:10；
5) obtained coating paste is passed through by polypropylene of the extrusion coated mode coated in 16 μ m-thicks/poly- using single side coating
Ethylene/polypropylene composite membrane matrix surface, single side coating thickness are 4 μm, and membrane is obtained after drying.
Membrane made from the present embodiment includes the polypropylene, polyethylene/polypropylene composite film matrix and painting that thickness is 16 μm
Cloth is in 4 μm of composite coatings of matrix single side；Composite coating includes the ultra-fine glass containing hydroxyl that the polypropylene wax of 60wt.% coats
The water soluble polymer of glass fiber (coating thickness of polypropylene wax is 2 μm), the water based emulsion of 30wt.% and 10wt.% increases
Thick dose；Wherein, the average diameter of the ultra-fine fibre glass containing hydroxyl is 500nm, and the fusing point of polypropylene wax is 130 DEG C, molecule
It measures as 10000, average grain diameter is 1 μm；Water based emulsion is polyvinylidene fluoride and the mixture (mass ratio of the two of pure third latex
For 1:1), water soluble polymer thickener is that (mass ratio of the two is 1 for the mixture of polyvinyl alcohol and sodium carboxymethylcellulose:
1)。
Embodiment 7
The preparation process of the present embodiment membrane is：
1) it is the ultra-fine fibre glass containing hydroxyl in mass ratio 1 of 2000nm by average diameter:10 ratio is added to
Polythene wax emulsion that solid content is 40% (average grain diameter of polyethylene wax is 3 μm, and fusing point is 110 DEG C, molecular weight 8000,
Solvent is deionized water) in, after stirring and impregnating 60min, filtration drying obtains polyethylene wax coating thickness and is 5 μm containing
The ultra-fine fibre glass of hydroxyl；
2) by water and water-soluble sodium carboxymethylcellulose in mass ratio 98.5:1.5 are added in mixer grinder, make carboxylic
Sodium carboxymethylcellulose pyce is completely dissolved, and obtains the aqueous solution of sodium carboxymethylcellulose；
3) ultra-fine fibre glass containing hydroxyl that polyethylene wax coats is proportionally added into sodium carboxymethylcellulose water
In solution, primary slurry is obtained after stirring；
4) pure third latex is added in into primary slurry, the strainer filtering through 150 mesh after stirring evenly obtains coating paste；
The quality of polyethylene wax coats in coating paste the ultra-fine fibre glass containing hydroxyl, pure third latex and sodium carboxymethylcellulose
Than for 95.5:4:0.5；
5) obtained coating paste is coated in the polyethylene film base of 9 μ m-thicks using single side coating by intaglio printing mode
Body surface face, single side coating thickness are 6 μm, and membrane is obtained after drying.
Membrane made from the present embodiment includes the polyethylene film matrix that thickness is 9 μm and is coated on polyethylene film matrix one side
6 μm of composite coatings；The ultra-fine fibre glass containing hydroxyl that the polyethylene wax that composite coating includes 95.5wt.% coats is (poly-
The coating thickness of ethylene waxes is 5 μm), pure third latex of 4wt.% and the sodium carboxymethylcellulose of 0.5wt.%；Wherein, contain
The average diameter of the ultra-fine fibre glass of hydroxyl is 2000nm, and the fusing point of polyethylene wax is 110 DEG C, and molecular weight 8000 is average
Grain size is 3 μm.
Embodiment 8
The preparation process of the present embodiment membrane is：
1) it is the ultra-fine fibre glass containing hydroxyl in mass ratio 1 of 5000nm by average diameter:10 ratio is added to
(average grain diameter of polytetrafluoroethylmodified modified polypropylene wax is 5 μ to the polytetrafluoroethylmodified modified polypropylene wax emulsion that solid content is 40%
M, fusing point are 160 DEG C, and molecular weight 30000, solvent is deionized water) in, after stirring and impregnating 60min, filtration drying obtains
Polytetrafluoroethylmodified modified polypropylene wax coating thickness is 5 μm of the ultra-fine fibre glass containing hydroxyl；
2) by water and water-soluble carboxyethyl cellulose in mass ratio 98.5:1.5 are added in mixer grinder, make carboxylic second
Base cellulose is completely dissolved, and obtains the aqueous solution of carboxyethyl cellulose；
3) ultra-fine fibre glass containing hydroxyl for coating polytetrafluoroethylmodified modified polypropylene wax is proportionally added into carboxylic
In ethyl cellulose aqueous solution, primary slurry is obtained after stirring；
4) ethylene-vinyl acetate copolymer is added in into primary slurry, the strainer filtering through 150 mesh after stirring evenly obtains
To coating paste；The ultra-fine fibre glass containing hydroxyl of polytetrafluoroethylmodified modified polypropylene wax cladding, ethylene in coating paste-
The mass ratio of acetate ethylene copolymer and carboxyethyl cellulose is 90:5:5；
5) obtained coating paste is coated in the poly- inclined difluoro of 12 μ m-thicks using single side coating by intaglio printing mode
Vinyl film matrix surface, single side coating thickness are 6 μm, and membrane is obtained after drying.
Membrane made from the present embodiment includes the PVDF membrane matrix and be coated on poly- inclined difluoro that thickness is 12 μm
6 μm of composite coatings of vinyl film matrix single side；What the polytetrafluoroethylmodified modified polypropylene wax that composite coating includes 90wt.% coated
The ethylene of ultra-fine fibre glass (coating thickness of polytetrafluoroethylmodified modified polypropylene wax is 5 μm), 5wt.% containing hydroxyl-
The carboxyethyl cellulose of acetate ethylene copolymer and 5wt.%；Wherein, the average diameter of the ultra-fine fibre glass containing hydroxyl is
5000nm, the fusing point of polytetrafluoroethylmodified modified polypropylene wax is 160 DEG C, and molecular weight 30000, average grain diameter is 5 μm.
Comparative example 1
The membrane of this comparative example is the polyethylene film of no composite coating, and thickness is 16 μm.
Comparative example 2
Membrane made from this comparative example include the polyethylene film matrix that thickness is 16 μm and be coated on 1 μm of matrix two sides it is multiple
Close coating；The ultra-fine fibre glass containing hydroxyl that composite coating includes 85wt.% (coats without polymer-wax, contains hydroxyl
The average diameter of the ultra-fine fibre glass of base is 1000nm), the carboxymethyl cellulose of the styrene-acrylic latex of 10wt.% and 5wt.%
Sodium.
Comparative example 3
Membrane made from this comparative example includes the polyethylene film matrix that thickness is 16 μm and 1 μm of pottery for being coated on matrix two sides
Porcelain coating；Ceramic coating includes the inorganic oxide aluminium powder (average grain diameter is 1.2 μm) of 85wt.%, the styrene-acrylic latex of 10wt.%
With the sodium carboxymethylcellulose of 5wt.%.
Membrane properties are tested
Following performance test is carried out to the membrane of Examples 1 to 6 and comparative example 1~3：
1) thermal contraction test：Test condition is that membrane sample 1h is toasted at 105 DEG C, calculates the thermal contraction of each group membrane sample
Rate, the results are shown in tables 1；
2) puncture strength is tested：Membrane sample is fixed on universal testing machine during test, with the needle apparatus of 2mm diameters
Membrane sample is stabbed with the speed of 50mm/min, records stress-strain diagram, draws the puncture strength value of membrane sample, every group of sample
Product retest 5 times, the results are shown in tables 1；
3) closed pore temperature is tested：The membrane sample being dipped in electrolyte is put into fixture during test, sealing is placed on drum
In wind drying box, oven temperature is arranged to 155 DEG C；Started to warm up from room temperature, and using electrochemical workstation simultaneously monitor every
The temperature-resistance variation relation of membrane sample, when resistance suddenly there are two the more than order of magnitude transition when corresponding temperature be every
Film closed pore temperature, test result is as shown in table 1 and Fig. 1；
4) liquid absorption amount is tested：Membrane sample is cut into certain size during test, is infiltrated on 0.5h in electrolyte at normal temperatures,
The weight difference of unit area membrane sample is liquid absorption amount before and after infiltration, and acquired results, which are listed in, is shown in Table 1.
The membrane properties test result of table 1, Examples 1 to 8 and comparative example 1~3
It can be seen from Table 1 that：
1) compared with comparative example 1：
The membrane of the embodiment of the present invention 1~8 to coat the ultra-fine glass containing hydroxyl because there are polymer-wax in composite coating
Glass fiber and having in terms of thermal contraction performance significantly improves, so as to effectively reduce battery under the high temperature conditions when the thermal contraction
Caused short-circuit risks；
Membrane of the embodiment of the present invention 1~8 with composite coating relative contrast's example 1 on puncture strength also has to a certain degree
Ground improves, therefore the ability of its puncture such as resistance to impurity and burr in the techniques such as winding is enhanced, and advantageously ensures that battery
Security performance；
The diaphragm closed pore temperature of the embodiment of the present invention 1~8 is less than comparative example 1, this is because the membrane of Examples 1 to 8 is answered
It closes there are polymer-wax in coating, after temperature rises to polymer-wax fusing point (less than diaphragm matrix in itself), polymer-wax will
Progressively melt-flow and it is inhaled between the ultra-fine fibre glass containing hydroxyl and in the micropore of barrier film base material, and comparative example
1 is the polyethylene diagrams for not designing composite coating, when temperature reach 130 DEG C when, diaphragm closed pore and internal resistance is made to raise suddenly, pass through
Just start to flow and cause short circuit after the fusing of certain time membrane, while internal resistance declines, as shown in Figure 1；
In addition, the membrane of the embodiment of the present invention 1~8 relative contrast's example 1 in terms of liquid absorption amount increased, this is because its
The skeleton that the ultra-fine fibre glass containing hydroxyl in coating is woven into has the liquid-adsorption layer of larger aperture, it is thus possible to receive more
More electrolyte is conducive to improve the cycle performance of battery core；Meanwhile the polymer-wax of fiber surface is coated on due to functional official
The presence that can be rolled into a ball also increases the compatibility with electrolyte；
2) compared with comparative example 2, the membrane difference of the embodiment of the present invention 1~8 is introducing polymer-wax group in coating
Divide and closed pore temperature is substantially reduced；This is because when temperature reaches the fusing point of polymer-wax, it will progressively melt stream
It moves and is inhaled between the ultra-fine fibre glass containing hydroxyl and in the micropore of barrier film base material, so as to hinder moving for lithium ion
It moves, its internal resistance is made to increase suddenly；When temperature reaches 130 DEG C or so of the melting temperature of barrier film base material, barrier film base material can be into one
Step melts and causes internal resistance (as shown in Figure 1) in a slight decrease；Additionally due to the presence of polymer-wax component, the embodiment of the present invention 1
~8 membrane relative contrast's example 2 in terms of liquid absorption amount also has lesser degree of increase；But in terms of thermal contraction and puncture strength,
The presence or absence of polymer-wax component is smaller on the membrane influence of same thickness, such as embodiment 6 and comparative example 2；
3) compared with comparative example 3, the membrane difference of the embodiment of the present invention 1~8 is containing hydroxyl in coating using cladding
For the ultra-fine fibre glass of base instead of inorganic oxide aluminium, this does not make it in thermal contraction and puncture strength performance in bad
Gesture is but provided with closed pore temperature lower due to the meltbility of polymer-wax, due to the ultra-fine fibre glass containing hydroxyl and
The absorbency of polymer-wax and with higher liquid absorption amount, so having more advantage on cycle performance.
Battery performance test
The membrane sample of Examples 1 to 3 and comparative example 1~3 is assembled into battery with anode, cathode and electrolyte respectively,
And reference numeral is S1~S3 (S represents embodiment) and D1~D3 (D represents comparative example)；To six groups of batteries progress following at room temperature
Ring performance test (rate of charge 0.7C, discharge-rate 0.5C), test result is as shown in Figure 2.
As can be seen from Figure：Number is the polyethylene diagrams that membrane used in the battery of D1 is no composite coating,
Cycle performance is relatively worst；The battery that number is D2 is with respect to D3 cycle performance of battery more preferably the reason is that diaphragm matrix surface coats
The ultra-fine fibre glass containing hydroxyl there is the liquid-adsorption layer of larger aperture, therefore more electrolyte can be received, improve electricity
The cycle performance of core.In addition, the battery that number is S1~S3 is respectively provided with some superiority, this difference with respect to the cycle performance of D2 batteries
There are polymer-wax bags for the ultra-fine fibre glass containing hydroxyl for not being primarily due in the membrane composite coating of Examples 1 to 3
Coating, since polymer-wax is the organic matter of low molecular weight, the excellent glass fibre of the corrosive power of resistance to organic electrolyte comes relatively
It says, polymer-wax has better compatibility with electrolyte, therefore can absorb and be swollen and retain more electrolyte, so as to follow
Advantage is had more in ring performance.
It is S1~S3 to number and four groups of batteries of D1 overcharge test, rate of charge 1C, cell voltage 6V, survey
Test result difference is as seen in figures 3-6.As can be seen from the figure：Number is that membrane used in the battery of D1 is no composite coating
Polyethylene diagrams, during overcharging, voltage and current is held essentially constant early period, but internal temperature gradually rise until every
After 125 DEG C of film fusing point, membrane first shrinks re-melting, ultimately results in battery short circuit, and electric current steeply rises, batteries caught fire, and temperature is high
Up to 350 DEG C or so (as shown in Figure 6)；And the battery for being S1~S3 is numbered during overcharging, voltage and temperature raise simultaneously, when
When voltage rises to 6V, temperature rises to 95~120 DEG C nearby, the polymer-wax on the ultra-fine fibre glass surface containing hydroxyl is coated on
Start to melt and block diaphragm micro-hole, cut off lithium ion tunnel so that temperature and electric current simultaneously decline, and ensure that the safety of battery
Work is (as seen in figures 3-5).
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out appropriate change and modification.Therefore, the invention is not limited in specific embodiment disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In used some specific terms, but these terms are merely for convenience of description, do not limit the present invention in any way.
Claims (7)
1. a kind of membrane, including porous diaphragm matrix and the composite coating being coated at least one surface of diaphragm matrix,
It is characterized in that：The composite coating includes the ultra-fine fibre glass containing hydroxyl of polymer-wax coating modification and aqueous breast
Glue, for coating the fusing point of the polymer-wax of the ultra-fine fibre glass containing hydroxyl as 80~160 DEG C, the polymer-wax cladding
Content of the modified ultra-fine fibre glass containing hydroxyl in composite coating is 60~95.5wt.%, and water based emulsion is compound
Content in coating is 4~30wt.%, a diameter of 0.5~5 μm of the ultra-fine fibre glass containing hydroxyl, length 0.1
~5mm；Polymer-wax is 1~5 μm in the coating thickness that the ultra-fine fibre glass surface containing hydroxyl is formed, the compound painting
Layer further includes the water soluble polymer thickener of 0.5~10wt.%.
2. membrane according to claim 1, it is characterised in that：Average grain diameter of the polymer-wax before cladding is 0.1
~5 μm.
3. membrane according to claim 1, it is characterised in that：The polymer-wax is selected from polyethylene wax, polypropylene wax, gathers
At least one of ethylene oxide wax, modified polyethylene wax, modified polypropylene waxes and ethylene-propylene copolymer wax.
4. membrane according to claim 1, it is characterised in that：The thickness of the composite coating is 2~5 μm.
5. membrane according to claim 1, it is characterised in that：The fusing point of the polymer-wax is 100~150 DEG C.
A kind of 6. method for preparing membrane according to any one of claims 1 to 5, it is characterised in that comprise the following steps：
1) ultra-fine fibre glass containing hydroxyl is proportionally added into the polymer-wax lotion that solid content is 20~50%, stirred
After mixing and impregnating fully, filtration drying obtains the ultra-fine fibre glass containing hydroxyl of polymer-wax coating modification；
2) water and water soluble polymer thickener are proportionally added into mixer grinder, are completely dissolved thickener, obtained
The aqueous solution of thickener；
3) ultra-fine fibre glass containing hydroxyl by polymer-wax coating modification made from step 1) is proportionally added into step
2) in aqueous thickener solution made from, primary slurry is obtained after stirring；
4) water based emulsion is added in into the primary slurry that step 3) obtains, is filtered after stirring evenly through 150 mesh filter screens, obtain coating
Slurry；
5) coating paste that step 4) obtains is coated in the surface of diaphragm matrix by way of intaglio printing or extrusion coated,
Membrane is obtained after drying.
7. a kind of lithium ion battery, including positive plate, negative plate and the membrane being interval between adjacent positive piece and negative plate,
It is characterized in that：The membrane is membrane according to any one of claims 1 to 5.
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| CN109428035B (en) * | 2017-08-31 | 2020-11-06 | 比亚迪股份有限公司 | Battery diaphragm, preparation method thereof and lithium ion battery |
| KR102280606B1 (en) * | 2018-01-05 | 2021-07-22 | 주식회사 엘지에너지솔루션 | Separator Comprising CMC, Particle-Type Binder, and Soluble-Type Binder |
| CN108598342A (en) * | 2018-03-28 | 2018-09-28 | 上海恩捷新材料科技股份有限公司 | A kind of battery diaphragm, lithium ion battery and preparation method thereof |
| CN110903504A (en) * | 2019-10-31 | 2020-03-24 | 安徽国风塑业股份有限公司 | Superfine glass fiber, preparation method and application thereof, and polyimide film |
| CN111081947B (en) * | 2019-12-25 | 2022-07-29 | 武汉中兴创新材料技术有限公司 | Preparation method of gel polymer coating diaphragm and diaphragm |
| CN114696038A (en) * | 2020-12-30 | 2022-07-01 | 山东海科创新研究院有限公司 | Polyolefin composite diaphragm coated with organic emulsion, preparation method of polyolefin composite diaphragm and lithium ion battery |
| CN114050372A (en) * | 2021-10-26 | 2022-02-15 | 惠州锂威新能源科技有限公司 | Diaphragm for lithium ion battery and preparation method and application thereof |
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| CN103247770A (en) * | 2013-04-25 | 2013-08-14 | 东莞新能源科技有限公司 | Lithium-ion battery separator and manufacturing method thereof |
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| KR20140029691A (en) * | 2012-08-29 | 2014-03-11 | 주식회사 엘지화학 | Separator for electrochemical device comprising core-shell particles, electrochemical device comprising the same, and method for preparing the separator |
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| CN101226994A (en) * | 2007-12-21 | 2008-07-23 | 成都中科来方能源科技有限公司 | Non-woven cloth increasing micropore polymer diaphragm and usage as well as preparation method thereof |
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